JP4622660B2 - Adsorption element - Google Patents

Description

  The present invention relates to an adsorption element, and more particularly, to an adsorption element used as an adsorption rotor in an adsorption heat pump that performs heat transfer using an adsorbent and various air conditioning systems that perform dehumidification and humidification using an adsorbent.

  Adsorption heat pumps and desiccant systems are systems that use adsorption and desorption functions of adsorbents to control heat transfer and humidity. For example, various cooling devices that use low-temperature exhaust heat in cogeneration systems, air conditioning units, humidity control systems Applies to devices. And about the adsorption | suction element used for said adsorption | suction heat pump and a desiccant system, the thing of a rotor structure is examined variously in order to improve adsorption | suction capability and to achieve size reduction of an apparatus.

  The rotor-structured adsorbing element includes a cylindrical adsorbing element in which an adsorbent is held in a cylindrical honeycomb structure having a large number of venting cells on the peripheral surface, and an air-permeable cell on the end face. Two columnar adsorbing elements formed by holding an adsorbent in a columnar honeycomb structure provided with a large number of have been proposed as "dehumidifying elements". A plurality of honeycomb sheets in which a row of cells is formed by stacking corrugated sheets on a flat sheet are laminated.

A cylindrical honeycomb structure uses a plurality of columnar laminates that are formed by laminating the above honeycomb sheets along the height direction and whose end faces are formed in a substantially fan shape, and the end faces are the honeycomb structure. It is manufactured by connecting columnar laminates in an annular shape so as to be positioned on the end face. On the other hand, a columnar honeycomb structure is manufactured by winding the honeycomb sheet around a core material or sequentially laminating the honeycomb sheets around the core material. The cylindrical honeycomb structure has a structure in which honeycomb sheets are sequentially stacked in the axial direction, and the columnar honeycomb structure has a structure in which honeycomb sheets are sequentially stacked in the radial direction.
JP 2004-209420 A

  The conventional rotor structure adsorption element is a combination of a flat sheet and a corrugated sheet, and the honeycomb structure has a structure in which these are laminated, and the manufacturing process of the honeycomb structure as a substrate is complicated. Therefore, there is a problem that the manufacturing cost cannot be reduced sufficiently. In particular, since a cylindrical adsorbing element is manufactured by manufacturing a large number of columnar laminated bodies and then connecting them in a ring shape to manufacture a honeycomb structure, the manufacturing process is further complicated.

  In addition, since the conventional adsorption element combines a flat sheet and a corrugated sheet, the opening shape of each cell is actually a substantially triangular shape, and each corner on the base side is an acute angle with a small angle. Therefore, there is a problem in that the air flow rate of each cell is smaller than the opening area, and the adsorption performance cannot be fully exhibited with respect to the total amount of adsorbent held. Furthermore, since the cylindrical adsorption element has a gap between the laminated bodies connected in the honeycomb structure or the outer peripheral surface of the honeycomb structure does not become a complete circumferential surface, Air may leak to the side, and air may not sufficiently pass through each cell, further reducing the adsorption performance.

  The field of application of the adsorption element is in the direction of expanding to small devices such as home air conditioners. In such a field, an adsorption element having a more general purpose and excellent characteristics is desired. An object of the present invention is to provide an adsorption element having an improved rotor structure that can be produced at a lower cost and that can exhibit higher adsorption performance.

  In order to solve the above-described problems, in the present invention, as the structure of the honeycomb structure serving as the base material of the adsorption element, a substantially corrugated plate shape obtained by developing a laminate of a large number of sheets formed in a rectangular flat plate shape. By adopting the laminated structure of only the sheet, the manufacturing process is simplified, and the opening shape of the cells of the honeycomb structure is formed in a substantially hexagonal shape by the laminated structure, thereby improving the ventilation efficiency. I made it.

  That is, the first gist of the present invention is a cylindrical adsorbing element in which an adsorbent is held in a cylindrical honeycomb structure provided with a large number of ventilation cells on the peripheral surface, the honeycomb structure However, the opening element of each cell is formed in a substantially hexagonal shape by providing a structure in which only a substantially corrugated sheet is laminated along the circumferential direction.

The second gist of the present invention is a columnar adsorbing element in which an adsorbent is held in a columnar honeycomb structure provided with a large number of ventilation cells on the end face, and the honeycomb structure includes It has a structure in which only substantially corrugated sheets are laminated along the circumferential direction , and a large number of sheets formed in a rectangular flat plate shape are laminated, and the front and back of each sheet are fixed in parallel with one side of the sheet. The side on which the cell opens when a laminate is formed by joining adjacent sheets to each other in a large number of linear joints set at a pitch and shifted by 1/2 pitch on the front and back sides. The opening shape of each cell is formed in a substantially hexagonal shape by expanding the stacked body in a state in which the other two parallel stacked surfaces adjacent to the stacked surface are curved . Adsorption element featuring To.

  According to the adsorbing element of the present invention, the honeycomb structure has a laminated structure of only substantially corrugated sheets, and a honeycomb structure can be easily produced by developing a laminated body of a large number of rectangular flat plates. Therefore, the manufacturing cost can be further reduced, and the opening shape of each cell is formed in a substantially hexagonal shape by the laminated structure in the honeycomb structure, so that the ventilation efficiency can be improved and the adsorption performance can be further improved. .

  Although the embodiment of the adsorption element according to the present invention will be described with reference to the drawings, the description of the constituent elements described below is a representative example of the embodiment of the present invention, and the present invention is not limited to these contents. Absent.

  FIG. 1 is a perspective view showing the outer shape of a cylindrical adsorption element according to the present invention and a partially enlarged view showing the shape of a cell. FIG. 2 is a perspective view showing an outer shape of a columnar adsorption element according to the present invention and a partially enlarged view showing a cell shape. Moreover, FIGS. 3-7 is a figure which shows the manufacturing method of the honeycomb structure as a base material. In these drawings, FIG. 3 is a partial perspective view showing a method of joining the sheets in the production of the sheet laminate, and FIG. 4 is a partial perspective view showing the outer shape of the sheet laminate. 5 is a partial side view of the laminate showing the deformation state of the sheet and the shape of the cell formed when the laminate of the sheet is expanded, and FIG. 6 is a laminate in the production of a cylindrical honeycomb structure. FIG. 7 is a perspective view showing a method for developing a laminate in the production of a columnar honeycomb structure.

  The adsorption element of the present invention is used as an adsorption rotor in various adsorption heat pumps and humidity control systems. As is well known, the adsorption heat pump is a system that pumps heat by using the phase change of adsorbate such as water and alcohol accompanying the adsorption / desorption phenomenon of the adsorbent, and it is low quality without using auxiliary power. Since thermal energy can be operated as a heat source, it can be applied to various systems such as cogeneration systems that require energy saving to generate cold or warm heat.

  In addition, the humidity control system includes a desiccant cooling device for cooling in warehouses, etc., a large desiccant air conditioner installed as building equipment, and a dehumidifier including small dehumidifiers and humidifiers installed indoors. It is configured as an air conditioner or humidifier air conditioner, etc., using the adsorption / desorption action of the adsorbent, removing moisture from the indoor air to be humidity adjusted or the air supplied to the room, and discharging it to the outdoors, It is a system that adsorbs moisture from outdoor air or air that is exhausted to the outside and supplies it to indoor air that should be humidity-adjusted or supplied to the room, and adjusts humidity using excess low-quality heat energy Can be done.

  The adsorbing element of the present invention is formed in a cylindrical shape or a columnar shape, depending on the structure of the device to which it is applied. The adsorbing element indicated by reference numeral (1A) in FIG. 1 is a cylindrical element that adsorbs and desorbs adsorbate vapor and water vapor by being configured to allow ventilation from the outer peripheral surface to the inner peripheral surface or from the inner peripheral surface to the outer peripheral surface. 2 is a columnar element that adsorbs and desorbs solute vapor and water vapor by being configured to be able to vent from one end face to the other end face.

  First, the cylindrical adsorption element (1A) shown in FIG. 1 will be described. The adsorbing element (1A) is configured by holding an adsorbent on a cylindrical honeycomb structure (1a) having a large number of ventilation cells (4) provided on the peripheral surface. In the adsorption element (1A), the honeycomb structure (1a) has a structure in which only the substantially corrugated sheet (31) is laminated along the circumferential direction, so that each cell (4) The opening shape is substantially hexagonal.

  The honeycomb structure (1a) is formed in a strip shape and a substantially corrugated sheet (31) having a zigzag shape with respect to the longitudinal direction aligns the longitudinal direction in parallel with the axis of the honeycomb structure. And a structure in which a large number of layers are stacked along the circumferential direction. In the cell (4) formed on the peripheral surface of the honeycomb structure (1a), the convex portions of the adjacent substantially corrugated sheet (31) have a predetermined width (a linear joint portion (21) described later). The opening shape is formed in a substantially hexagonal shape. In the honeycomb structure (1a), the arrangement direction (X) of the cells (4) formed by the adjacent substantially corrugated sheet (31) is the direction along the longitudinal direction of the sheet (31), that is, The direction along the axis of the honeycomb structure.

  The honeycomb structure (1a) is formed by laminating a large number of sheets (31) formed in a rectangular flat plate shape (for example, a band shape), and at a constant pitch parallel to one side of the sheet on the front and back of each sheet (31). And the laminated body (3) (FIG. 4) which joins each adjacent sheet | seat (31) mutually in many linear joining parts (21) (refer FIG. 3) set in the state shifted | deviated 1/2 pitch on the front and back. And the laminated body (3) is developed in a state in which the two parallel laminated surfaces on the side where the cells (4) open are curved.

  The manufacturing method of the honeycomb structure (1a) and the adsorption element (1A) will be described with reference to FIGS. 3 to 6. In order to manufacture the honeycomb structure (1a), first, as shown in FIG. A flat sheet (2) large enough to produce the honeycomb structure (1a) is prepared, these are laminated, and each adjacent flat sheet (2) is joined at a predetermined site.

  The flat sheet (2) is finally formed into the substantially corrugated sheet (31) described above, and the flat sheet (2) holds a powdery adsorbent. A fiber sheet with the flexibility to obtain is used. In the present invention, the fibrous sheet refers to a sheet made of an aggregate of inorganic or organic fibrous substances, and the fibrous substances may be intertwined with each other. For example, fillers having a large aspect ratio, nonwoven fabrics, and the like are also included in the concept of “fibrous”. By using the fibrous sheet as described above, adsorption elements of various sizes can be easily manufactured, and vibration resistance can be improved. In the present invention, the state of holding the adsorbent means that the adsorbent powder penetrates into the sheet (31) by impregnating the honeycomb structure with slurry containing the adsorbent as described later. The state in which the adsorbent layer is formed on the surface of the sheet (31), in other words, the state in which the adsorbent is supported.

  Specifically, the constituent material of the fibrous sheet includes ceramic fibers mainly composed of silica / alumina, glass fibers, carbon fibers produced from raw materials containing carbon such as PAN and tar, and fibrous clay substances. And mineral fibers, organic silicon fibers manufactured from organosilicon polymers, metal fibers manufactured from metals such as Fe, Cu, Al, Cr, and Ni. Examples of the chemical fiber include fibers such as acrylic, polyethylene, polypropylene, polyurethane, polyclar, nylon, rayon, vinylon, vinylidene, polyvinyl chloride, acetate, and polyester. Natural fibers such as cellulose, silk, and cotton can also be used.

  In particular, in consideration of moldability, handleability, and manufacturing cost, the material for the fibrous sheet is preferably a nonwoven fabric. Examples of such a nonwoven fabric include chemical fiber-based nonwoven fabrics such as rayon, nylon, polyester, polyethylene, polypropylene, acrylic, vinylon, cupra, and aromatic polyamide. The chemical fiber nonwoven fabric as described above may be either a single fiber or a laminate of two or more fibers. As is well known, the nonwoven fabric is manufactured by a manufacturing method such as a wet method, a dry method, a spun bond method, a melt blow method, a chemical bond method, a thermal bond method, or a needle punch method. The normal thickness of the fibrous sheet is usually 40 to 600 μm, preferably 50 to 400 μm.

  The flat sheet (2) shown in FIG. 3 is laminated, for example, about 100 to 1000 sheets depending on the size of the honeycomb structure (1a) and the size of the cells (4). And each flat sheet (2) is laminated | stacked sequentially with respect to each adjacent sheet | seat (2) by joining methods according to materials, such as heat welding, ultrasonic welding, or adhesion | attachment using an adhesive agent, when laminating | stacking. Joined at a predetermined site. In the flat sheet (2), as a joint portion with each adjacent sheet (2), the front and back of each sheet (2) are shifted at a constant pitch parallel to one side of the sheet and ½ pitch on the front and back. A large number of linear joints (21) are set. The interval between the linear joint portions (21) on one surface of the sheet (2) is about 2 to 15 mm, and when the linear joint portion (21) is set at the above-mentioned interval, one cell (4) Can be formed in a cell having a maximum diagonal of about 3 to 25 mm.

  After laminating the flat sheet (2), as shown in FIG. 4, the flat sheet (such as a belt having a length (L) and a width (W) is formed on each end face on the laminating direction side. The laminate in 2) is cut to produce a rectangular parallelepiped laminate (3). That is, in the laminate (3), a large number of strip-like sheets (31) of a predetermined size formed from the flat sheet (2) are laminated, and each adjacent sheet (31) is the linear joint (21). Are joined together. The length (L) in the laminate (3) corresponds to the axial length of the honeycomb structure (1a), and the width (W) is the difference between the outer diameter and the inner diameter (cylinder thickness) of the honeycomb structure (1a). Equivalent to. Although it differs depending on the device to which the adsorption element (1A) is applied, the size of the honeycomb structure (1a), that is, the size of the laminated body (3) is usually about 60 to 400 mm in length (L), The width (W) is about 10 to 60 mm.

  When the laminate (3) obtained as described above is expanded in the laminating direction (vertical direction in FIG. 4), as shown in FIG. 5, each belt-like sheet (31) is substantially corrugated. A large number of cells (4) are opened on two parallel laminated surfaces along the length (L) of the laminated body (3). In addition, the arrow of the code | symbol (Y) in FIG. 4 has shown the communication direction of the cell (4) formed when a laminated body (3) is expanded, and FIG. The cell (4) to be formed is shown, and the arrow (X) in FIG. 5 indicates the extending direction of each sheet (31) and the arrangement direction of the cells (4) formed by each adjacent sheet (31). Show.

  Therefore, in the present invention, as shown in FIG. 6, the opening of the cell (4) that appears when the laminate (3) is used and expanded, is formed on the peripheral surface of the honeycomb structure (1a). In a state of being positioned, that is, when the laminate (3) is expanded, the cylinder (3) is developed by expanding the laminate (3) in a state in which the two parallel laminate surfaces on the side where the cell (4) opens are curved. The honeycomb structure (1a) is formed. In other words, when unfolding the laminate (3), the laminate (3) is placed so that one long side of the belt-like sheet (31) is located on the inner periphery and the other long side is located on the outer periphery. Bend in a ring. And the sheet | seat (31) corresponded to the both end surfaces of the lamination direction of a laminated body (3) is joined.

  When the honeycomb structure (1a) is manufactured, the laminate (3) is formed by directly laminating a number of strip-like sheets (31) formed in advance in length (L) and width (W). In doing so, they may be produced by joining them at the above-described linear joint (21).

  The honeycomb structure (1a) obtained as described above has a structure in which only a substantially corrugated sheet (31) is laminated along the circumferential direction, and the opening shape of each cell (4) is approximately six. It is formed in a square shape. The adsorbing element (1A) of the present invention is manufactured by impregnating the honeycomb structure (1a) with a slurry composed of an adsorbent, a binder, and a solvent, followed by drying treatment with hot air or the like. That is, the adsorption element (1A) of the present invention has a structure in which an adsorbent is fixed to each sheet (31) of the honeycomb structure (1a) with a binder. The adsorbent and the binder will be described later.

  Next, the columnar adsorption element (1B) shown in FIG. 2 will be described. The adsorbing element (1B) is configured by holding an adsorbent on a columnar (for example, short-axis columnar) honeycomb structure (1b) provided with a large number of ventilation cells (4) on the end surface. And in adsorption element (1B), honeycomb structure (1b) is provided with the structure which laminated | stacked only the substantially corrugated sheet | seat (31) along the circumferential direction of each cell (4). The opening shape is substantially hexagonal.

  As shown in FIG. 2, the honeycomb structure (1b) is formed in, for example, a short-axis columnar shape, and a rotation shaft is mounted at the center. The short-axis cylindrical honeycomb structure (1b) has a substantially corrugated sheet (31) formed in a strip shape and bent in a zigzag manner with respect to the longitudinal direction, and the longitudinal direction of the honeycomb structure (1b) has a radius of the honeycomb structure. A large number of structures are stacked along the circumferential direction. In the cell (4) formed on the end face of the honeycomb structure (1b), the convex portions of the adjacent substantially corrugated sheet (31) have a predetermined width (the width of the linear joint portion (21)). By joining, the opening shape is formed in a substantially hexagonal shape. In the honeycomb structure (1b), the arrangement direction (X) of the cells (4) formed by the adjacent substantially corrugated sheet (31) is the direction along the longitudinal direction of the sheet (31), that is, The direction along the radius of the honeycomb structure.

  The honeycomb structure (1b) is formed by stacking a large number of rectangular flat plate sheets (31) formed in a rectangular flat plate shape (for example, a belt shape), and parallel to one side of the sheet on the front and back of each sheet (31). A laminate (3) formed by joining adjacent sheets (31) to each other at a large number of linear joints (21) (see FIG. 3) set at a constant pitch and shifted by 1/2 pitch on the front and back sides. ) (See FIG. 4), when this is expanded, the laminated body (3) is expanded in a state in which the other two parallel laminated surfaces adjacent to the laminated surface on the side where the cell (4) opens are curved. It is composed by doing.

  The manufacturing method of the honeycomb structure (1b) and the adsorbing element (1B) is as shown in FIG. 3 to FIG. 5 and FIG. 7. When the honeycomb structure (1b) is manufactured, the laminate (3) is manufactured. The steps up to here are the same as those of the above-described cylindrical honeycomb structure (1a). That is, the honeycomb structure (1b) uses a flat sheet (2) shown in FIG. 3 made of the same constituent material as the material of the sheet (31) deformed into a substantially corrugated plate, After producing the laminated body (3) as shown in FIG. 4 by the same method, the laminated body (3) is developed and manufactured.

  In the present invention, when the cylindrical honeycomb structure (1b) is manufactured, as shown in FIG. 7, the laminate (3) is used, and the cell (4) that is expressed when the laminate (3) is expanded is used. Two other parallel laminated surfaces adjacent to the laminated surface on which the cell (4) is opened when the opening is positioned on the end face of the honeycomb structure (1b), that is, when the laminated body (3) is expanded. The honeycomb structure (1b) is configured by developing the stacked body (3) in a state in which (the stacked surface on the width (W) side of the sheet (31) in FIG. 4) is curved. In other words, when unfolding the laminate (3), the laminate (3) is placed so that one short side of the belt-like sheet (31) is located on the inner periphery and the other short side is located on the outer periphery. Bend in a ring. And the sheet | seat (31) corresponded to the both end surfaces of the lamination direction of a laminated body (3) is joined.

  When the honeycomb structure (1b) is manufactured, the laminated body (3) is directly laminated with a belt-like sheet (31) formed in advance with a predetermined size, like the honeycomb structure (1a). At the same time, they may be produced by joining them at the linear joint (21) when they are laminated.

  The honeycomb structure (1b) obtained as described above has a structure in which only the substantially corrugated sheet (31) is laminated along the circumferential direction, and the opening shape of each cell (4) is approximately six. It is formed in a square shape. The adsorbing element (1B) of the present invention is similar to the adsorbing element (1A) described above, after impregnating the honeycomb structure (1b) with a slurry composed of an adsorbent, a binder and a solvent, It is manufactured by performing the drying process by. That is, the adsorption element (1B) of the present invention has a structure in which an adsorbent is fixed to each sheet (31) of the honeycomb structure (1b) with a binder.

  Next, the slurry used for production of the adsorption elements (1A) and (1B) of the present invention, and the adsorbent and binder contained therein will be described. The slurry impregnated in the honeycomb structures (1a) and (1b) is composed of an adsorbent, a binder, and a solvent such as water. In addition, other substances such as a stabilizer may be added to the extent that the effects of the present invention are not impaired. For example, the blending ratio of the above three-component slurry is as follows. That is, the adsorbent is 5 to 60% by weight, the binder is 0.1 to 50% by weight, and the solvent is 30 to 94.9% by weight. Preferably, the adsorbent is 10 to 45% by weight, the binder is 1 to 30% by weight, and the solvent is 40 to 80% by weight. Furthermore, the weight ratio of the solvent to the adsorbent is usually in the range of 1 to 20%, preferably 1.25 to 5%, and it is preferable that the amount of binder does not exceed the amount of adsorbent.

  The reason why the ratios of the adsorbent, binder and solvent in the slurry are defined as described above is as follows. That is, when the ratio of the adsorbent to the solvent exceeds the upper limit, the slurry concentration is too high and the adsorbent may not be impregnated smoothly. On the other hand, if the lower limit is not reached, the amount of adsorbent that can be impregnated at a time is reduced, which is inefficient. Further, when the amount of the binder exceeds the amount of the adsorbent, there is a binder that is not effectively used, which may cause undesirable aggregation of particles. On the other hand, when the value is below the lower limit, the function as a binder cannot be sufficiently achieved. In order to impregnate the sheets (31) of the honeycomb structures (1a) and (1b) with the slurry as described above, the honeycomb structures (1a) and (1b) are usually immersed in the slurry.

  The binder for holding the adsorbent in the honeycomb structures (1a) and (1b) may be either an organic or inorganic binder. Examples of the organic binder include acrylic resins and vinyl acetate resins. , Styrene resins, various copolymer resins, olefin resins, epoxy resins, urethane resins, phenol resins, silicone resins and other adhesives dissolved in organic solvents, or acrylic resin emulsions, vinyl acetate resins Examples thereof include emulsion adhesives obtained by emulsifying resin components such as emulsions, styrene resin emulsions, various copolymer resin emulsions, olefin resin emulsions, epoxy resin emulsions, urethane resin emulsions, and phenol resin emulsions.

  Various binders can be selected from the viewpoints of slurry stability, heat resistance and slurry viscosity adjustment, and particularly from the viewpoint of thermal stability, an epoxy resin adhesive is used. More specifically, an epoxy resin emulsion adhesive is preferable. Depending on the sheet material and the molding method, two or more kinds of adhesives may be used. Examples of the inorganic binder include silica sol, alumina sol, titania sol, and zirconia sol. Furthermore, for organic and inorganic binders (slurries described later), fibrous materials such as metal fibers and carbon fibers with good thermal conductivity, aluminum, copper, silver, etc. to improve thermal conductivity in the sheet (31). Metal powder or graphite may be added.

On the other hand, examples of the adsorbent retained on the honeycomb structures (1a) and (1b) include zeolite, silica gel, alumina, activated carbon, polymer sorbent, and ion exchange resin. Among these, zeolite that can easily adsorb adsorbate vapor and water vapor and can be easily desorbed in a low temperature range is preferable, and crystalline aluminophosphates containing at least Al and P in the skeleton structure are particularly preferable. From the viewpoint of increasing the diffusion of the adsorbate vapor and water vapor in the individual particles of the adsorbent, the particle size of the adsorbent is usually 0.1 to 300 microns, preferably 0.5 to 250 microns, and preferably 0.5 to 250 microns. Preferably it is 1 to 200 microns, most preferably 2 to 100 microns. The basis weight of the adsorbent for each sheet (31) of the honeycomb structures (1b) and (1a) is 5 to 200 g / m ² . The amount of adsorbent retained per volume of the honeycomb structures (1b) and (1a) is preferably 30 to 200 g / l.

  The above aluminophosphates (hereinafter abbreviated as ALPOs as appropriate) are crystalline aluminophosphates defined by IZA (International Zeolite Association). In the crystalline aluminophosphate, atoms constituting the skeletal structure are aluminum and phosphorus, and a part thereof may be substituted with other atoms. Among these, from the viewpoint of adsorption characteristics, (I) Me-aluminophosphate in which aluminum is partially substituted with a heteroatom Me1 (where Me1 belongs to the third or fourth period of the periodic table, 2A group, 7A group, 8 Group, 1B group, 2B group, 3B group (except at least one element selected from Al), (II) Me-aluminophosphate in which phosphorus is substituted with hetero atom Me2 (where Me2 is a period) 4B group elements belonging to the third or fourth period of the table) or (III) Me-aluminophosphate in which both aluminum and phosphorus are substituted with heteroatoms Me1 and Me2, respectively.

  Me may be contained alone or in combination of two or more. Preferable Me (Me1, Me2) is an element belonging to the third and fourth periods of the periodic table. Me1 preferably has an ionic radius of 3 or more and 0.8 nm or less in a divalent state, and more preferably has an ionic radius of 0.4 or more and 7 nm or less in a divalent or tetracoordinate state. Among these, from the viewpoint of ease of synthesis and adsorption characteristics, at least one element selected from Fe, Co, Mg, and Zn is preferable, and Fe is particularly preferable. Me2 is a group 4B element belonging to the third or fourth period of the periodic table, and is preferably Si.

Further, as the aluminophosphates, those having a framework density (FD) of 13 T / nm ³ or more and 20 T / nm ³ or less are usually used. The lower limit of the framework density is preferably 13.5 T / nm ³ or more, and more preferably 14 T / nm ³ or more. On the other hand, the upper limit of the framework density is preferably 19 T / nm ³ or less. If the framework density is less than the above range, the structure tends to be unstable, and the durability is lowered. On the other hand, if the framework density exceeds the above range, the adsorption capacity becomes small and it is not suitable for use as an adsorbent. The framework density (unit: T / nm ³ ) means T atoms (number of elements constituting a skeleton other than oxygen per 1 nm ^{3 of} zeolite) present per unit volume (nm ³ ).

  The structure of aluminophosphates includes AEI, AEL, AET, AFI, AFN, AFR, AFS, AFT, AFX, ATO, ATS, CHA, ERI, LEV, and VFI, as indicated by the code defined by IZA. Among these, from the viewpoint of adsorption characteristics and durability, those having an AEI, AEL, AFI, CHA, and LEV structure are preferable, and those having an AFI and CHA structure are particularly preferable.

  Among the above aluminophosphates, SAPO-34 and FAPO-5 are particularly preferable as the adsorbent. One or two or more kinds of ALPOs can also be used in combination. The production conditions of FAPO and SAPO are not particularly limited, but are usually produced by hydrothermal synthesis after mixing an aluminum source, a phosphorus source, and a Me source such as Si and Fe as required, and a template. Is done. ALPOs can be synthesized using known synthesis methods described in, for example, JP-B-1-57041, JP-A-2003-183020, JP-A-2004-136269, and the like.

  According to the adsorbing elements (1A) and (1B) of the present invention as described above, the honeycomb structures (1a) and (1b) are provided with the laminated structure of only the substantially corrugated sheet (31), and the rectangular structure Since the honeycomb structures (1a) and (1b) can be easily produced by developing the laminate (3) (see FIG. 4) of a large number of flat sheets (31), the manufacturing cost can be further reduced. And since the opening shape of each cell (4) is formed in the substantially hexagon shape by said laminated structure in honeycomb structure (1a) and (1b), ventilation efficiency can be improved and adsorption | suction performance can be improved more. .

  In the adsorption elements (1A) and (1B) of the present invention, when the sheet (31) of the honeycomb structures (1a) and (1b) is composed of a fibrous sheet, particularly a non-woven fabric, for example, the particle size By stacking a large amount of adsorbents having a smaller particle diameter of 10 μm or less, the adsorption / desorption capability can be further increased, and the device itself can be further miniaturized. Furthermore, when the above-mentioned specific zeolite is used as the adsorbent, adsorbate vapor and water vapor can be easily adsorbed and desorbed in a narrow temperature range and can be easily desorbed in a low temperature range. The adsorption heat pump and the humidity control system, particularly the small dehumidifying air conditioner and the humidifying air conditioner can be suitably used.

Example 1:
A cylindrical adsorption element (1A) shown in FIG. 1 was produced. As the honeycomb structure (1a), a structure having an outer diameter of 120 mm, an inner diameter of 80 mm, and a height of 85 mm was produced. The honeycomb structure (1a) is obtained by laminating 182 sheets (31) made of polyester non-woven fabric. Each sheet (31) has a vertical and horizontal length of 95 mm × 20 mm and a normal thickness of 280 μm. Met. Further, when the laminate (3) was developed to form a cylinder, the sheets (31) at both ends were joined with an adhesive, and a mesh cylindrical core was inserted into the cylinder so that the inner diameter was 80 mm. . The cells (4) formed on the peripheral surface of the obtained honeycomb structure (1a) are substantially hexagonal cells having an average maximum diagonal length of 6.9 mm, and the honeycomb structure (1a) is effective. The volume was 534 cm ³ .

  In holding the adsorbent in the honeycomb structure (1a), 800 g of SAPO-34 having an average particle size of 5 μm obtained by synthesis and pulverization was synthesized by the method described in Example 2 of JP-A-2003-183020. The honeycomb structure (1a) is immersed in a slurry prepared by mixing 210 g of an emulsion binder containing 38 wt% of a silica-modified acrylic copolymer resin and 1190 g of water, and the liquid is drained while being pulled up and rotated. The sheet (31) was impregnated with the SAPO-34 slurry. Then, the honeycomb structure (1a) was charged in an oven at 120 ° C. for 30 minutes and dried by heating, and then the adsorbing element (1A) was obtained by extracting the previously inserted mesh cylindrical core material. .

  With respect to the above adsorbing element (1A), when the amount of adsorbent was measured by weight measurement, it was confirmed that 54 g of SAPO-34 was held in the honeycomb structure (1a). And about adsorption | suction ability of adsorption | suction element (1A), after leaving for 20 minutes under the airflow of temperature 20 degreeC, humidity 50%, and wind speed 2m / s, as a result of measuring adsorption amount by weight measurement, 13.2g of water | moisture content was obtained. Adsorption was confirmed.

Comparative Example 1:
In order to manufacture a conventional cylindrical adsorbing element, a laminate of a flat sheet and a corrugated sheet was produced, and an attempt was made to produce a cylindrical honeycomb structure by a method of developing in a curved state in the same manner as in the examples. It was. That is, a rectangular parallelepiped honeycomb structure was first manufactured by alternately laminating a flat ceramic sheet having a normal thickness of 120 μm and a corrugated corrugated ceramic sheet. The height (length corresponding to the axial length of the cylindrical body) of such a rectangular parallelepiped honeycomb structure is 85 mm, the length (length corresponding to the circumferential direction of the cylindrical body) is 377 mm, and the thickness (cell communication length). (Length corresponding to) was 20 mm. Each cell was a substantially triangular cell, and the height of the opening of the cell (corrugated height) was 4 mm, and the arrangement pitch was 6 mm. Next, when the above rectangular parallelepiped honeycomb structure was curved in a cylindrical shape so that the parallel sides in the length direction became the inner and outer circumferences, many cracks and cell collapse occurred, and the cylindrical honeycomb structure was I couldn't make it.

Comparative Example 2:
In order to manufacture a conventional cylindrical adsorbing element, a plurality of laminates of a flat sheet and a corrugated sheet were prepared, and an attempt was made to produce a cylindrical honeycomb structure by a method of connecting them. That is, eight columnar laminates were first produced by alternately laminating a flat ceramic sheet having a normal thickness of 120 μm and corrugated corrugated ceramic sheets. The height (length corresponding to the axial length of the cylindrical body) of each columnar laminate is 85 mm, the length (length corresponding to the circumferential direction of the cylindrical body) is 31.4 mm, and the thickness (cell communication length) (Length corresponding to) was 20 mm. In addition, each cell in the columnar laminate was a substantially triangular cell, and the height of the opening of the cell (corrugated height) was 4 mm, and the arrangement pitch was 6 mm.

Next, the eight laminated bodies are gathered and arranged in a substantially annular shape so that the parallel sides in the length direction become the inner and outer circumferences, and the donut plates having an outer diameter of 120 mm and an inner diameter of 80 mm are arranged at both end faces of the annular aggregate. By fixing with, a substantially cylindrical honeycomb structure was produced. In such a honeycomb structure, the cross-sectional shape of the central space portion was actually an octagon. Further, the area of the inner peripheral surface of the honeycomb structure was substantially the same as that in Example 1, but the effective volume was 427 cm ³ , which was 20% smaller than that in Example 1.

  With respect to the honeycomb structure manufactured as described above, SAPO-34 was held as an adsorbent by the same method as in Example 1 to produce a substantially cylindrical adsorbing element. And about such an adsorption | suction element, when the quantity of the adsorbent was measured by weight measurement, it was confirmed that 42g of SAPO-34 is hold | maintained at the honeycomb structure. And about the adsorption | suction capability of an adsorption | suction element, as a result of measuring adsorption amount by the method similar to Example 1, it was confirmed that only 10.0 g of water | moisture content is adsorb | sucked.

It is the perspective view which shows the external shape of the cylindrical adsorption | suction element based on this invention, and the elements on larger scale which show the shape of a cell. It is the perspective view which shows the external shape of the column-shaped adsorption | suction element based on this invention, and the elements on larger scale which show the shape of a cell. It is a figure which shows the manufacturing method of the honeycomb structure as a base material, and is a partial perspective view which shows the joining method of each sheet | seat in preparation of the laminated body of a sheet | seat. It is a figure which shows the manufacturing method of the honeycomb structure as a base material, and is a partial perspective view which shows the external shape of the laminated body of a sheet | seat. It is a figure which shows the manufacturing method of the honeycomb structure as a base material, and is a partial side view of the laminated body which shows the deformation | transformation state of the sheet | seat when the laminated body of a sheet is expanded, and the shape of the cell formed. It is a figure which shows the manufacturing method of the honeycomb structure as a base material, and is a perspective view which shows the expansion | deployment method of the laminated body in preparation of a cylindrical honeycomb structure. It is a figure which shows the manufacturing method of the honeycomb structure as a base material, and is a perspective view which shows the expansion | deployment method of the laminated body in preparation of a cylindrical honeycomb structure.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1A: Cylindrical adsorption element 1a: Cylindrical honeycomb structure 1B: Columnar adsorption element 1b: Columnar honeycomb structure 2: Flat sheet 21: Linear joint 3: Laminate 31: Square plate Sheet 4: cell L: length of laminated body W: width of laminated body X: arrangement direction of cells formed by adjacent sheets Y: air flow direction of cells formed by laminated body

Claims (6)

  A cylindrical adsorbing element in which an adsorbent is held in a cylindrical honeycomb structure having a large number of ventilation cells on its peripheral surface, and the honeycomb structure surrounds only a substantially corrugated sheet. An adsorption element characterized in that the opening shape of each cell is formed in a substantially hexagonal shape by providing a structure laminated in a direction.   The honeycomb structure is formed by laminating a large number of sheets formed in a rectangular flat plate shape, and is set on the front and back of each sheet at a constant pitch parallel to one side of the sheet and shifted by 1/2 pitch on the front and back. When the laminated body is formed by joining adjacent sheets to each other in the linear joint portion of the linear joint, the parallel laminated surface on the side where the cells open is curved to expand the laminated body. The adsorbing element according to claim 1, which is configured by: A columnar adsorbing element in which an adsorbent is held in a columnar honeycomb structure provided with a large number of ventilation cells on the end face, the honeycomb structure only in the circumferential direction of a substantially corrugated sheet In addition, a large number of sheets formed in a rectangular flat plate shape are stacked, and the front and back of each sheet are shifted at a constant pitch parallel to one side of the sheet and ½ pitch on the front and back. When a laminated body formed by joining adjacent sheets to each other in a large number of linear joint portions set in a state is used, and when this is expanded, another parallel two adjacent to the laminated surface on the side where the cells open An adsorbing element characterized in that the opening shape of each of the cells is formed in a substantially hexagonal shape by expanding the laminated body in a state in which two laminated surfaces are curved . The adsorption element according to any one of claims 1 to 3 , wherein the sheet constituting the honeycomb structure is a fibrous sheet. The adsorption element according to claim 4 , wherein the fibrous sheet is made of a nonwoven fabric. Adsorbent, adsorbing device according to any one of claims 1-5 to the backbone structure is a zeolite containing aluminum and phosphorus.

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